Alkynyl esters of {60 -alkoxy-{60 -phenyl alkenoic acid

ABSTRACT

(R4 and n are as defined above) and A is a group of -COOR3, which is useful as synergist for insecticides, especially for a cyclopropane-carboxylate or a carbamate type insecticide.   (R4 is hydrogen, halogen, a C1-4 alkyl or methylenedioxy, and n is an integer of 1 to 5), R2 is a C1-6 alkyl, a C3-6 alkenyl or a C3-6 alkynyl, R3 is a C1-6 alkyl, a C3-6 alkenyl or a C3-6 alkynyl, (provided that R2 is a C3-6 alkynyl when R3 is a C1-6 alkyl), and A is a group of -COOR3 or -CH2OR3, provided that R1 is a C1-6 alkyl, a C2-6 alkenyl, a C3-6 alkynyl, a C3-6 cycloalkyl or benzyl when A is a group of -CH2OR3 (R3 is as defined above,) and R3 is a C4-6 alkenyl or a C4-6 alkynyl when R1 is a group of   WHEREIN R1 is a C1-6 alkyl, a C2-6 alkenyl, a C3-6 alkynyl, a C3-6 cycloalkyl, benzyl, thienyl or a group of   A compound of the formula,

United States Patent Kitamura et al.

1 Feb. 4, 1975 1 1 ALKYNYL ESTERS .OF

a-ALKOXY-a-PHENYL ALKENOIC ACID [73] Assignee: Sumitomo ChemicalCompany,

Limited, Osaka, Japan [22] Filed: Dec. 13, 1971 [21] Appl. No.: 207,542

[30] Foreign Application Priority Data Dec. 29, 1970 Japan 45-124365 Aug. 6, 1971 Japan 46-59784 Aug. 16, 1971 Japan 46-62412 [52] US. CL... 260/473 A, 260/332.2 A, 260/340.5, 260/611 A, 424/189, 424/275, 424/282, 424/308, 424/341 [51] Int. Cl. C07c 69/76 [58] Field of Search 260/473 A [56] References Cited UNITED STATES PATENTS 3,176,019 3/1965 Campbell et a1 260/473 A 3,702,864 11/1972 Kitamura et a1. 260/473 A OTHER PUBLICATIONS March, Adv. Organic Chemistry, McGraw-Hill & C0. (1968), pp. 316.

Primary ExaminerLorraine A. Weinberger Assistant Examiner-John F. Terapane Attorney, Agent, or Firm-Stevens, Davis, Miller & Mosher [57] ABSTRACT A compound of the formula,

C A l -OR (11 2 wherein R is a C alkyl, 21 C alkenyl, a C alkynyl, a C cycloalkyl, benzyl, thienyl or a group of (R is hydrogen, halogen, a C alkyl or methylenedioxy, and n is an integer of l to 5), R is a C alkyl, 11 C alkenyl or a C alkynyl, R is a C alkyl, a C alkenyl or a C alkynyl, (provided that R is a C alkynyl when R is a C, alkyl), and A is a group of -COOR or -CH OR provided that R, is a C alkyl, a C alkenyl, a C alkynyl, a C cycloalkyl or benzyl when A is a group of -CH OR (R is as defined above,) and R is a C alkenyl or a C alkynyl when R, is a group of (R and n are as defined above) and A is a group of -COOR which is useful as synergist for insecticides, especially for a cyclopropane-carboxylate or a carbamate type insecticide.

3 Claims, No Drawings 1 ALKYNYL ESTERS OF a-ALKOXY-a-PHENYL ALKENOIC ACID The present invention relates to a novel phenyl acetic acid derivative and a synergist containing the same.

More particularly, this invention relates to a novel phenylacetic acid derivative represented by the formula (l),

wherein R is a C alkyl, a C alkenyl, a C alkynyl, a C cycloalkyl, benzyl, thienyl or a group of (R is hydrogen, halogen, a C alkyl or methylenedioxy, and n is an integer of l to 5), R is a C alkyl, a C alkenyl or a C alkynyl, R is a C alkyl, a C alkenyl or a C alkynyl, (provided that R is a C alkynyl when R is a C alkyl), and A is a group of COOR or -CH OR provided that R, is a C alkenyl, a C alkynyl, a C cycloalkyl or benzyl when A is a group of Cl-l OR (R is as defined above), and R is a C alkenyl or a C alkynyl when R is a group of (R, and n are as defined above) and A is a group of COOR;,, and relates to a synergist containing at least one said phenyl acetic acid derivative.

So far, it is known that sesamine and the like contained in sesame oil may be used for enhancing the insectidical activities of pyrethroide type insecticides.

Based upon the knowledge that the sesamine contained in sesame oil has methylenedioxyphenyl group in the molecule, there have been synthesized various compounds having such group, and as the synergist for pyrethrin, there are now widely used a-[2- (butoxyethoxy)-ethoxy]-4,5-methylene-dioxy-2- propyltoluene (hereinafter referred to as piperonyl butoxide), l,2-methylenedioxy-4-[2-(octyllsulfinyl)- propyl]benzene (hereinafter referred to as sulfoxide), 4-( 3 ,4-methylenedioxy-phenyl )-5-methyll ,3-dioxane (hereinafter referred to as safroxane), etc. There are other kinds of synergist on the market including N-(Z- ethylhexyl)bicyclo[2,2,l ]-hept-5-eneanhydro-phthalic acid-2,3-dicarboxyimide (trade mark McLaughlin Gormley King Co.), and the like.

They have, however, both merits and demerits, for example, the piperonyl butoxide most widely used now among the known synergists has prominent synergistic effect on natural pyrethrin, but somewhat inferior on allethrin and other synthetic pyrethroids, and MGK- 264 has more excellent synergistic effect on allethrin than that on natural pyrethrin.

MGK-264,

Thus, an object of the present invention is to provide a novel compound having prominent synergistic effect on various cyclopropanecarboxylate type insecticides as well as on natural pyrethrin.

Another object of the present invention is to provide a novel compound having prominent synergistic effect on carbamate type insecticides.

Other objects of the present invention is to provide a process for producing such synergistic compound having low toxicity to mammals at a low production cost.

These objects can be accomplished by providing the phenylacetic acid derivative represented by the formula (l) mentioned above, and a process for producing the same which comprises reacting a compound of the formula (II), or a reactive derivative thereof,

wherein R R and n are as defined above, X is hydroxy, a halogen or OR (R is as defined above) and Y is -CH OH, CH Hal (Hal is a halogen), -CH- OR -COOR (R is as defined above) or COOH, with a compound of the formula (Ill), or a reactive derivative thereof, I

(lll) wherein Z is hydroxy or a halogen, and R5 is the same meanings as R, or R The process of the present invention will be illustrated in more detail.

1. The reaction between an alkali metal salt, an ammonium salt, or a salt or organic tertiary base ofthe acid represented by the formula (ll), and the halide or tosylate of the alcohol represented by the formula (Ill) may be conducted in an inert solvent such as benzene, toluene, acetone and dimethylformamide at room temperature or under heating.

2. The reaction between the acid halide of the formula (ll) and the alcohol of the formula (III) may be conducted in an indert solvent such as benzene and toluene using as a dehydrogen halide agent an organic tertiary base such as pyridine and triethylamine at room temperature.

3. The reaction between the acid of the formula (ll) and the alcohol of the formula (lll) may be conducted in an inert-solvent such as benzene and toluene in the presence of a dehydrating agent at room temperature or under heating.

4. The reaction between the acid anhydride of the formula (ll) and the alcohol of the formula (III) may be conducted in an inert solvent at room temperature.

5. The reaction beteen the a-hydroxy acid represented by the formula (ll) in which both of hydroxyl and carboxyl are substituted by an alkali metal, and the halide or tosylate of the alcohol represented by the formula (lll) may be conducted in an inert solvent such as benzene, toluene and dimethylformamide at room temperature or under heating.

6. The reaction between the a-haloester or the a-haloether represented by the formula (II) and the alcohol of the formula (III) ln which the hydroxy is substituted by an alkali metal, may be conducted in an inert solvent such as benzene, toluene and dimethylformamide. at room temperature or under heating. When the alcohol used is methanol or ethanol, it is advantageous to use methanol or ethanol as the solvent.

7. The reaction between the alcohol of the formula (ll) in which the hydroxy is substituted by an alkali metal, and the halide or tosylate of the alcohol of the formula (III) may be conducted in an inert solvent such as benzene, toluene and dimethylformamide at room temperature or under heating.

According to the above mentioned process. the following compounds can be obtained.

l. Alkynyl a-alkyloxyphenyl acetates subbstituted by an alkyl, an alkkenyl. an alkynyl, a cycloalkyl, a phenyl. a benzyl or a thienyl group at a-position, and the acetates in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

2. Alkynyl a-alkenyloxyphenylacetates substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a phenyl, a benzyl or a thienyl group at a-position, and the acetates in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

3. Alkynyl a-alkynyloxyphenylacetates substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a phenyl, a benzyl or a thienyl group at a-position, and the acetates in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

4. Alkenyl a-alkyloxyphenylacetates substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a phenyl, a benzyl or a theinyl group at a-position, and the acetates in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

5. Alkenyl a-alkenyloxyphenylacetates substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a phenyl, a benzyl or a thienyl group at a-position, and the acetates in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

6. Alkenyl a-alkynyloxyphenylacetates substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl. a phenyl, a benzyl or a thienyl group, and the acetates in Cornpo and which the phenyl group is substituted by at least one member ofalkyl groups, halogen atoms and methylenedioxy group.

7. Alkyl a-alkynyloxyphenylacetates substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a phenyl, a benzyl, or a thienyl group at a-position, and the acetates in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

8. Alkynyl a-alkoxyphenethyl ethers substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl, or benzyl at a-position, and the ethers in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

9. Alkynyl a-alkenyloxyphenethyl ethers substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl, or benzyl at a-position, and the ethers in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

I0. Alkynyl a-alkynyloxyphenethyl ethers substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl or benzyl at a-position, and the ethers in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

1 1. Alkenyl a-alkoxyphenethyl ethers substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl or benzyl at a-positiorl, and the ethers in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

12. Alkenyl a-alkenyloxyphenethyl ethers substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl or benzyl at a-position, and the ethers in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

I3. Alkenyl a-alkynyloxyphenethyl ethers substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl or benzyl at a-position, and the ethers in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

14. Alkyl a-alkynyloxyphenethyl ethers substituted by an alkyl, an alkenyl, an alkynyl, a cycloalkyl, or benzyl at a-position, and the ethers in which the phenyl group is substituted by at least one member of alkyl groups, halogen atoms and methylenedioxy group.

Among the present compounds mentioned above, typical examples, and formulae and physical properties thereof are enumerated as follows, and it is needless to say that the present invention is not limited only thereto.

Physical Formula property C!H2CH2CH3 Q0 coo0H c==oH 11 1.5136

methoxyphenylacetate Compound Continued Physical Formula. property C CH H3 I CH 6-0 COOCHZCICH 5 1.5071

OCH

Propargyl a-(iso-propyl)-amethoxyphenylacetate Q o cooon czcn n5 1.5184

OCH

Propargyl cz-allyI-oc-methoxyphenylacetate cl: 000011 02011 n5 1.5142

OCH

Propargyl oc-butenyl-amethoxyphenylacetate Propargyl a-allyl-aethoxyphenylacetate CH CH CH 3 g 25 C COOCH CCH n 1-5112 OCH Propargyl a-(iso-lutyU-ocmethoxyphonylacetate 25 Q-( COOCH2C. CH n 1.5055

OCHZCHZCH3 Propargyl y -(l l-pz-opyloaxwphenylacetate I OCH Proparg-yl cx(n-hexyl)a methoxyphcnylacetate Compound Con tinued Physical Formula property OCH Propargyl a-cyclohexyl-amethoxyphenylacetate y a-allyl-amethoxyphenylacetate c-ooocn ci CH n3 1.5589

I OCH Propargyl oz-benzyl-amethoxyphenylacetate C-COOCH CECH n 1.5489

OCH OH Propargyl a-benzyl-cc-ethoxyphenyl' acetate C-COOCH CH= CH n 1.5486

I OCH Allyl oc-benzyl-a-methoxyphenylacetate CC0OCH C;=. CH n5 1.5698 1 OCH Propargyl a-(2-thienyl)-amethoxyphenylacetate CH C=CH I 25 (l-COOCH CH=CH n 1.5143 OCH Allyl a-propargyl-a-methoxyphenylacetate Continued Compound Formula OCH Propargyl a-cyclohexyl-a-methoxyphenethyl ether CIZH CH CH C-CH OCH C 5. CH

OCH C ECH Physical property Propargyl cxn-propyl )-a-propargyloxyphenethyl ether l G-q-CH OCH CECH OCH Propargyl a-benzyl-a-methoxyphenethyl ether CH CH CH OCH l-Butynyl an-propyl -a-me thoxyphenethyl ether qn ca cu Q (II-CHZOCHZCHZCHZCHZC a CH OCH l-Hexynyl a-(n-propyD-a-methoxyphenethyl ether The process of the present invention will be explained in more detail with reference to the following examples, which are not intended to limit the scope of the present invention EXAMPLE 1 A solution of 4.2, g of a-(iso-propyU-amethoxyphenyl acetic acid, 3.0 g of triethylamine and 2.6 g of propargyl bromide in 20 cc of dimethylformamide was stirred for 2 hours, whereby white precipitates were deposited. The reaction mixture was poured in water, and the resultant was subjected to extraction with ether. The extract was washed with an aqueous solution saturated with sodium chloride and dried over anhydrous sodium sulfate, and thereafter evaporation of ether gave 4.5 g of oil propargyl a-(iso-propyU-amethoxyphenylacetate, m, 1.507].

Elementary Analysis C (71) H (71) Calculated (as C H O 73.l5 7.37 Found 73.42 7.51

EXAMPLE 2 Elementary Analysis C (7? l H (/1 l Calculated (as CmH Ou) 74.39 7.02 Found 74.2) 694 EXAMPLE 3 Into a suspension of 0.75 g of 66 sodium hydrideparaffin inZO cc of dimethylformamide was added a solution of 5.6 g of allyl a-benzyl-a-hydroxyphenylacetate in 10 cc of dimethylformamide under cooling, and the mixture was stirred for 1 hour. Successively, methyl chloride was introduced into the mixture. The reaction mixture was poured in ice-water and the resultant was subjected to extraction with ether. The ether extract was washed with an aqueous solution saturated with sodium chloride, and dried over sodium sulfate. Thereafter, ether was distilled out and paraffin was removed,

stirred for 2 hours. The reaction mixture was poured into water, and the resultant was subjected to extraction with ether. The extract was washed with sodium bicarbonate solution and aqueous solution saturated with sodium chloride, and dried over sodium sulfate. Evaporation of ether gave 4.3 g of oily 3-butynyl a-phenyl-a-methoxyphenyl acetate, n 1.5574.

whereby 5.1 g oily allyl a-benzyl-a-methoxyphenylace- 10 Elementary Analysis tate, n f'" 1.5488 was obtained. c Wt) H W) Calculated (as C ,.H ,.O l 77.53 6.16 Found 77.71 6.08

Elementary Analysis 1 5 C (7c) H (71 Calculated (as am o 77.00 6.80 EXAMPLE 7 Found 76.88 6.68

Into a suspension of 0.75 g of 66 sodium hydrideparaffln in 20 cc of dimethylformamide was added 20 a solution of 3.8 g of a-allyl-a-methoxyphenethylal- EXAMPLE 4 cohol in l cc of dimethylformamide under cooling,

Elementary Analysis C ('7, i H (l Calculated (as H OM 77.00 6.80 Found 76.93 6.87

EXAMPLE Into a suspension of 1.5 g of 66 sodium hydrideparaffin in cc ofdimethylformamide was added a solution of 4.5 g of a-phenyl-a-hydroxyphenylacetic acid in 10 cc of dimethylformamide under cooling, and the mixture was stirred for 1 hour. Successively, 5.8 g of butynyl bromide was added thereto and the stirring was continued for 1 hour. The reaction mixture was poured in ice-water, and the resultant was subjected to extraction with ether. The ether extract was washed with an aqueous solution saturated with sodium chloride, and dried over sodium sulfate. Thereafter ether was distilled out and paraffin was removed to obtain 4.0 g of oily l-butynyl a-phenyl-a-(l-butynyloxy)phenylacetate, m, 1.5581.

Elementary Analysis C H (7a) Calculated (as C' H Cl- 79.49 6.06 Found 79.41 6.18

EXAMPLE 6 A solution of 4.8 g of a-phenyl'a-methoxyphenylacetic acid, 3.0 g of triethylamine and 4.0 g of tosylate of butynyl alcohol in 20 cc of dimethylformamide was and the mixture was stirred for 1 hour. Successively, 2.5 g of propargylbromide was added thereto and the stirring was continued for 1 hour. The reaction mixture was poured in ice-water, and the resultant was subjected to extraction with ether.

The ether extract waswashed with an aqueous solution saturated with sodium chloride and dried over sodium sulfate. Thereafter ether was distilled out and paraffin was removed to obtain 3.5 g of oily propargyl a-a1- lyl-a-methoxyphenethylether. 11,, 1.5197.

Elementary Analysis C H Calculated (as (,,\H.,,(),) 78.23 7.88 Found 78.16 7.79

The phenylacetic acid derivatives according to the present invention have prominent synergistic effects on natural pyrethrin as well as allelthrin and other various cyclopropanecarboxylic acid ester type insecticides, particularly prominent effect on N- chrysanthemoxymethyl-3,4,5,6-tetrahydrophthalimide (hereinafter referred to as tetramethrin).

In addition, the present phenylacetic acid derivatives are more excellent in the synergistic effect on allethrin, tetramethrin and 5-benzyl-3-furylmethyl chrysanthemate [hereinafter referred to as Chrysron, (a registered trade mark of Sumitomo Chemical Co., Ltd.)], compared with that of piperonyl butoxide which has been used most widely among the commercially available synergists.

Further, the present phenylacetic acid derivatives have prominent synergistic effects also on carbamate type insecticides such as carbaryl, and may be useful for the production of an insecticidal composition having broader effects for controlling injurious insects, because of their hormone activities on insects.

0 The synergistic effects of the present phenylacetic acid derivatives on the cyclopropanecarboxylic acid ester type insecticides and the carbamate type insecticides will be substantiated in the following referential example.

Referential Example Each mixture of natural pyrethrin, allethrin, tetramethrin, Chrysron or carbaryl with 5 times amount by weight based on the weight of said active ingredient of piperonyl butoxide or the present compounds l) to (27), or said active ingredient itself was adjusted to desired test concentration with use of acetone. and the killing effect was measured accordingto the method in Table Insecticide Synergist rm Ratio of enhancing (v/F y) the killing effect Tetramethrin 0.530 1.0 do. Piperonyl butoxide 0.129 4.1 do. Present compound 1) 0.068 7.8 do. do. (2) 0.061 8.7 do. do. (3) 0.064 8.3 do. do. (4) 0.071 7.5 do. do. (5) 0.042 12.5 do. do. (6) 0.066 8.0 do. do. (7) 0.067 7.9 Tetramethrin Present compound (8) 0.128 4.5 do. do. (9) 0.111 4.8 do. do. (10) 0.077 6.9 Tetramethrin 0.520 1.0 do. Piperonyl butoxide 0.121 4.3 do. Present compound (1 1) 0.046 1 1.3 do. do. (12) 0.052 10.0 do. do. (13) 0.050 10.4 do. do. (14) 0.064 8.1 do. do. (15) 0.060 8.7 do. do. (16) 0.055 9.5 do. do. v (17) 0.063 8.3 do. do. (18) 0.047 11.1 Tetramethrin 0.570 1.0 do. Piperonyl butoxide 0.146 3.9 do. Present compound (19) 0.067 8.5 do. do. (20) 0.053 10.8 do. do. (21) 0.060 9.5 do. do. (12) 0.056 10.2 do. do. (23) 0.085 6.7 do. do. (24) 0.054 10.6 do. do. (25) 0.065 8.8 do. do. (26) 0.081 7.0 do. do. (27) 0.081 7.0 Natural 0.400 1.0 Pyrethrin Piperonyl butoxide 0.077 5.2 do. Present compound (1) 0.082 4.9 do. do. (3) 0.079 5.1 do. do. (5) 0.071 5.6 Natural Pyrothrin 0.350 1.0 do. Piperonyl butoxide 0.071 4.9 do. Present compound (1 1) 0.054 6.5 do. do. (16) 0.064 5.5 Natural Pyrethrm 0.390 1.0 do. Piperonyl butoxide 0.076 5.1 do. Present compound (20) 0.056 7.0 do. do. (24) 0.058 6.7 Allethrin 0.560 1.0 do. Piperonyl butoxide 0.175 3.2 do. Present compound (1) 0.085 6.6 do. do. (3) 0.076 7.4 do. do. (5) 0.057 9.8 Allethrin 0.60 1.0 do. Piperonyl butoxide 0.167 3.6 do. Present compound (1 1) 0.060 10.0 do. do. (16) 0.083 7.2 Allethrin 0.610 1.0 do. Piperonyl butoxide 0.185 3.3 do. Present compound (20) 0.062 9.8 do. do. (24) 0.069 8.8 Chrysron 0.026 1.0 do. Piperonyl butoxide 0.021 1.2 do. Present compound l 1 1 l 3.4 Chrysron Present compound (3) 1 l 2 4 do. dd. (51 0.000 2.7 Chrysron 0.024 1.0 do. Piperonyl hutoxidc 0 |.3 do. Present compound 1 1 l J 0.0011 3.0 d do. 1101 0.000 2.7 Chrysron 0.027 1.0 Pipcronyl hutoxitlc 0.021 1.3 Prcscnt compound 0.010 2.7 do. a do. c (24) 0.013 2.1 Carharyl 5 or more 1.0

Pipcronyl hutoxidu 0.240 30.x or more Prescnt compound l I 02011 240 do. do. do. 131 0.104 35.x do. do. do. 151 0.161 31.0 dd. Carbaryl 5 or more 1.0

Piperonyl hutoxidc 0.20 25 or more Prescnt compound 1 l l 0,09 56 do. o do. 11(1 0.11 do.

which a small amount of the resulting preparation is attached to dorsum ofprotharum of housefly adults with use of a microcylinge. As the results. the lethal dose [the amount required for killing 7r of the flies (LD H is shown in the following table.

Table Continued insecticide Synergist LD, Ratio of enhancing (Y/Fly) the killing effect Carbaryl or more Lo do. Piperonyl butoxidc 0.262 I) or more do. Present compound (21)) 0.120 -11 do. do. do. (24) (l. l 28 3) do. 3.4-Dimethylphenyl-N- methylcarbamate 5 or more HI do. Piperonyl hutoxidc 0.836 6 or more do. Present compound l l i 0.278 18 do. do. do. (3) 0.273 18 do. do. do. (5) ".238 ll do. 3.4'Dimethyl phenyLN- methyl carbamate 5 or more I.()

do. Piperonyl hutoxide 0.63 8 or more do. Present compound l l) 0.21 24 do. do. do. (l6) 0.25 Ill do. 3,4-Dimcthyl phenyl-N- methylcarbamate 5 or more 1.0

do. Piperonyl butoxide 0.970 5 or more do. Present compound (20) 0.252 I) do. do. do. (24] 0.258 19 do.

Present compound 1 l J 2 or more do. (2] i. do. (3) do. do. (4) do. do. (5) do. do. (6) do. do. (7) do. do. 8) do. do. (1) do,

Present compound (10) Z or more do. 1 I) do. do. [11) do. do. l3) do. do. 14) do. do. 15) do. do. (16) do. do. l7) do. do. l 3) do. do. 19) do. do. (20) do. do. (ll do. do. (13) do. do. (23) do. do. (24) do. do. (25) do. do. (26) do. do. (27) do.

As is clear from the above Referential Example, the present compounds are effective as synergists for cyclopropanecarboxylate type insecticides and carbamate type insecticides, but the scope to which the present compounds may be applied is not limited thereto.

Compositions comprising one or more insecticides of the cyclopropanecarboxylic ester type and the carbamate type, as the active ingredients, and, in addition, one or more phenylacetic acid derivatives of the present invention in an amount of suitable times the .weight of said active ingredients, are specifically effective in controlling sanitary pests such as house flies, mosquitoes, cockroaches; rice plant pests such as rice stem borers, plant hoppers, leafhoppers; lepidopterous larvae, which are injurious to fruittrees and vegetables, such as larvae of cabbage worms, army worms, diamond-back moths, cut worms, etc.; plant parasitic mites; pantry pests such as rice weevils, almond moths, etc. Furthermore, said compositions are also effective in controlling other agricultural and sanitary pests, forest pests,

and pests for horticulture.

In the preparation of the insecticidal compositions, the active insecticides of the cyclopropanecarhoxylic ester type or the carbamate type, and the novel synergists of phenylacetic acid derivatives may be optionally formulated by use of usual adjuvants for insecticides into any form such as oil sprays, emulsifiable concentrates, wettable powders, dusts, granules, aerosols, mosquito coil, fumigants, dusts or solid preparations containing baits and other attractants, and any other form, although in some cases it is more convenient for formulation to use the active ingredients and synergists dissolved in advance in suitable solvents such as xylene, methyl-naphthalene, acetone, trichloroethane, and the like.

Under certain circumstances, the insecticial activities of said compositions can be further enhanced by simultaneous in corporation with piperonyl butoxide, sulfoxide, safroxane, MGK-264, 5-421 and other known synergists for pyrethroids, etc.

Multipurpose compositions can be formulated with said insecticidal compositions by the incorporation with other active ingredients such as organochlorine or organo-phosphorus insecticides, fungicides, miticides, herbicides, fertilizers, and other agricultural chemicals.

The preparative method and the effectiveness of the present insecticidal compositions will be further illustrated in the following Examples 8 to 27, and Test Examples l to 12, but it is needless to say that these examples are not intended to limit the scope of the present invention.

EXAMPLE 8 A mixture of 0.05 part of tetramethrin respectively together with each of 0.25 part of the present compounds l to (27) was dissolved individually in 2 parts of xylol, and the resultant was made the whole lOO parts with deodorized kerosene, where by each oil spray was obtained.

EXAMPLE 9 A solution of 0.05 part of N-chrysanthemoxymethyldimethylmaleimide, 0.15 part of the present compound and 0.] part of piperonyl butoxide in 5 parts of xylol was made the whole l00 parts with deodorized kerosene, whereby the oil spray was obtained.

EXAMPLE A mixture of 0.] part of 3-phenoxybenzyl chrysanthemate respectively together with each of 0.5 part of the present compounds (2), (3), (5). (ll), (l6) and was dissolved individually in 2 parts of xylol, and the resultant was made the whole 100 parts with deodorized kerosene, whereby each oil spray was obtained.

EXAMPLE I l A mixture of 0.05 part'of Chrysron respectively together with each of 0.25 part of the present compounds (2), (3), (5), (ll), (l3), (20) and (24) was dissolved individually in 2 parts of xylol, and the resultant was made the whole 100 parts with deodorized kerosene, whereby each oil spray was obtained.

EXAMPLE 12 A solution of 0.035 part of tetramethrin, 0.015 part of Chrysron and 015 part of the present compound (ll) in 2 parts of xylol was made the whole [00 parts with deodorized kerosene, whereby the oil spray was obtained.

EXAMPLE 13 A mixture of 1.5 parts of pyrethrum extract (containing 20 of pyrethrin), 1.5 parts of the present compound (2), 1 part of DDT, 5 parts of xylol and 6 parts of deodorized kerosene was introduced into an aerosol vessel, and a valve portionwas equipped to the vessel. Thereafter, 85 parts of a propellent (a liquified petroleum gas) was introduced under a pressure through the said valve portion, whereby the aerosol was obtained.

EXAMPLE 14 A mixture of 0.35 part of the d-trans isomer of tetramethrin, 0.05 part of Chrysron,- 1 part of the present compound (12), 6.6 parts of xylol and 7 parts of deodorized kerosene was ntroduced into an aerosol vessel, and a valve portion was equipped to the vessel. Thereafter, 85 parts of the same propellent as mentioned in Example ll was introduced under a pressure through the valve portion, whereby the aerosol was obtained.

-- EXAMPLE 15 EXAMPLE 16 A mixture of 0.3 part of tetramethrin respectively together with each of 1.5 parts of the present compounds (2), (3), (5), (ll) and (20) was dissolved individually in 20 parts ofacetone, and the resultant was stirred and mixed sufficiently with 98.2 parts of 300 mesh diatomaceous earth in a mixing and grinding machine. Successively, evaporation of acetone gave each dust.

EXAMPLE l7 A mixture of l part of Meobal (3,4-dimethylphenyl- N-methylcarbamate) respectively together with each of 3 parts of the present compounds (5), (l2) and (20) was dissolved individually in 20 parts of acetone, and the resultant was mixed sufficiently under stirring with 796 parts of 300 mesh talc in a mixing and grinding machine. Thereafter, evaporation of acetone gave each dust.

EXAMPLE 18 A mixture of 1 part of Bassa (2-sec-butylphenyl N- methylcarbamate) respectively together with each of 2 parts of the present compounds (5), (l l) and (20) was dissolved individually in 20 parts of acetone, and the resultant was mixed under stirring with 797 parts of 200 mesh talc in a mixing and grinding machine. Thereafter, evaporation of acetone gave each dusts.

EXAMPLE l9 A mixture of 5 parts of ipropargylfurfuryl chrysan themate, 20 parts of the present compound (20), 15 parts of Sorpol SM-200 (Trade mark of an emulsifier produced by Toho Chemical Co.) and 60 parts of xylol was mixed and dissolved under stirring to obtain the emulsifiable concentrate.

EXAM PLE 20 A mixture of 5 parts of d-trans isomer of Allethrin, 25 parts ofthe present compound l 3 l5 parts of Sorpol SM-200, and 55 parts of xylol was mixed and dissolved under stirring to obtain the emulsifiable concentrate.

EXAMPLE 2] A mixture of 5 parts of dl-cis isomer of Chrysron, 25

parts of the present compound (l6), 15 parts of Sorpol SM-200, and 55 parts of xylol was mixed and dissolved each other under stirring to obtain the emulsifiable concentrate.

EXAMPLE 22 A mixture of 15 parts of tetramethrin, 5 parts of dtrans isomer of Chrysron, 30 parts of the present compound (22), 5 parts of Sorpol SM-200 and 45 parts of 300 mesh talc was mixed sufficiently under stirring in a mixing and grinding machine to obtain the wettable powder.

EXAMPLE 23 A mixture of 0.4 g of allethrin respectively together with each of 1.2 g of the present compounds (1 l), (16) and (22) was dissolved individually in 20 ml of methanol, and the resultant was mixed homogeneously with 98.4 g ofa carrier for a mosquito coil (a mixture of tabu powder, mare and wood powder in the ratio of 3:5:1). After methanol was evaporated, 150 ml of water was added thereto, and the resultant was kneaded sufficiently, formulated and dried, whereby each mosquito coil was obtained.

EXAMPLE 24 A mixture of0.2 g of 5-propargyl-a-ethynylfuryl 2',2- '-dimethylcyclopropanecarboxylate and 0.8 g of the present compound (5) was dissolved in a suitable amount of chloroform, and the resulting solution was adsorbed in a surface of asbestos having an area of 2.5 cm X 1.5 cm and a thickness of 0.3 mm. Another asbestos having the same area and thickness as mentioned above was attached on the foregoing asbestos.

Thus, the fibrous insecticidal fumigant for an electric heating plate was obtained. There may be used other fibrous materials than asbestos such as pulp and the like, which have the effect equivalent to that of asbestos.

EXAMPLE 25 A mixture of parts .of 3'-phenoxybenzyl-2,2,3,3- tetramethylcyclopropane-1-carboxylate, 35 parts of the present compound (3), 5 parts of Sorpol SM-200 and 45 parts of 300 mesh talc was stirred sufficiently in a mixing and grinding machine, whereby the wettable mixing and grinding machine. Water was added thereto in an amount of 10 7c of said mixture. and the resulting mixture was granulated by means of a granulator and air-dried, whereby the granule was obtained.

Insecticidal activities of the present composition prepared above are substantiated in the following Test Examples.

TEST EXAMPLE 1 According to Campbell's turn table method [Soap and Sanitary Chemicals, Vol. 14, No. 6, 119 (1938)], 5 ml of each of the oil sprays obtained in Example 8 was sprayed, and one group of about 100 house fly adults was exposed to the descending mist for 10 minutes. Successively, the flies were fed and transferred in a thermostat to be allowed to stand at 27C, and after 24 hours, 90 or more of the flies were killed by any oil spray.

On the other hand, the test was made on 0.05 oil spray prepared according to the same procedure in Example 8 using singly tetramethrin to know the killing ratio of 52 Therefore the synergistic effect of the present compounds was confirmed.

TEST EXAMPLE 2 According to the procedure similar to that of Test Example 1, the tests were made on the insecticidal effects of the oil sprays obtained in Examples 9, 10, l l, and 12, whereby 90 or more of house flies were killed after 24 hours by each oil spray.

TEST EXAMPLE 3 According to the aerosol test method using Peet Gradys chamber (6 ft) [Soap and Chemical Specialities, Blue Book 1965)], the tests were made on insecticidal effects to house fly adults concerning the aerosols obtained in Examples l3, l4, and 15 and the results were powder was obtained. as shown in the following table.

lnseeticidal effects Amount sprayed Knock down ratio Mortality Composition g/l000ft 5 min. 10 min. 15 min. ("/0) Aerosol of Example 13 3.0 29 69 85 73 Aerosol of Example 14 3.1 42 81 97 94 Water base aerosol of 3.0 36 80 93 87 Example 15 TEST EXAMPLE 4 To the bottom ofa glass Petri dish of 14 cm in diameter, each of the dusts obtained in Examples 16 and 17 was uniformly dusted in a proportion of 2 g/m and butter was coated on the lower part of the dish, leaving an uncoated portion of 1 cm in width. Subsequently, a group of about 10 adults of German cockroaches was liberated in the dish and contacted with the dust for 10 5 minutes, thereafter the cockroaches were transferred to another vessel, were fed and were allowed to stand for 3 days, whereby 9O or more of the cockroaches were killed.

TEST EXAMPLE Onto young rice plants grown in a flower pot having about 2.5 inch of diameter, which had elapsed about 20 days after sowing, the dusts obtained in Examples l6, l7 and 18 were dusted in an amount ratio of 300 mg/pot with use ofa bell jar duster, and the whole was, 4 minutes thereafter, covered with a wire net. About 20 brown leafliopper adults were liberated therein, whereby 9O or more of the leafhoppers were killed after 24 hours by any dust.

TEST EXAMPLE 6 Into a (70 cm) glass chamber, about 50 house fly adults were liberated, and 0.7 ml of each emulsion prepared by diluting the emulsifiable concentrates obtained in Example 19, 20 and 21, to 50 times with water, was sprayed under 20 lb by means of a glass atomizer, whereby 90 or more of the house flies were knocked down within minutes. On next day, 90 or more of the house flies knocked down were killed.

TEST EXAMPLE 7 TEST EXAMPLE 8 Into a (70 cm) glass chamber, about 50 northern house mosquito adults were liberated, and the mosquito coils which were obtained in Example 23 and which were ignited on both ends, were placed respectively in the glass chamber, whereby 8O or more of the mosquitoes were knocked down within minutes by any coils.

TEST EXAMPLE 9 Into a (70 cm) gass chamber, about 50 house fly adults were lilerated, and the insecticidal fumigant for heating obtained in Example 24 was placed on an electric heating plate to be fumigated under heating in the chamber, whereby 80 or more of the house flies were knocked down within 20 minutes.

TEST EXAMPLE l0 The emulsifiable concentrates obtained in Examples 20 and 26 were diluted to 40,000 times with water, and

2 liters of the resulting emulsion ws introduced into a polystyrene case having 23 X 30 cm of area and 6 cm of depth. About 100 full grown larvae of northern house mosquitoes were liberated therein, whereby or more of the larvae were killed on next day by each emulsion.

TEST EXAMPLE ll Into a 14 liter volume polyethylene backet. was put 10 liters of water, and 0.5 g of the granule obtained in Example 27 .was added. After a day, about full grown larvae of northern house mosquitoes were liberated therein. As the results, it was observed that 90 7k or more of the larvae were killed within 24 hours.

TEST EXAMPLE l2 Into 100' g of unhulled rice, was mixed under sufficient stirring 100 mg of each dust obtained in Example 16, and the mixture was put into 100 ml Erlenmeyer flask. About 50 rice weevils were liberated therein, and the flask was covered and allowed to stand for a week, whereby 8O or more of rice weevils were killed.

What is claimed is:

1. A compound of the formula,

wherein R, is a C alkenyl, R is a C alkyl, and R is terminally unsaturated C alkyl. 2. A compound of the formula,

(M 011 CH C COOCHi' CH 3. A compound of the formula,

CH CH CH OCH CH 

1. A COMPOUND OF THE FORMULA,
 2. A compound of the formula,
 3. A compound of The formula, 